JPS6262872A - Electrically conductive coating agent and electrically conductive material using said agent - Google Patents

Abstract

PURPOSE:A novel electrically conductive coating agent, consisting of a binder resin, electrically conductive alkali metal titanate whiskers and solvent and capable of giving electrically conductive materials having improved reinforcing properties and deterioration resistance. CONSTITUTION:A coating agent obtained from (A) a binder resin, (B) electrically conductive alkali metal titanate whiskers, e.g. whiskers of an alkali metal compound expressed by the formula (M is Li, Na or K; a, b an x are real numbers as follows; 0<a<=8; 0<=b<=4; 0<x<2) or bronze alkali metal titanate, etc., particularly preferably potassium metal titanate whiskers having 0.2-0.5mum fiber diameter and 20-60 aspect ratio and (C) a solvent. The resultant coating agent is applied onto a mold releasable base material and dried or continuously applied to a film-forming base material and dried to afford the aimed electrically conductive material.

Description

[Detailed Description of the Invention] <Industrial Application Field> This invention relates to a conductive coating agent using a newly developed conductive alkali metal titanate whisker as a conductive material and a conductive "I" material using the same. I'll go.

<Prior art and its problems> Various conductive paints in which various conductive materials are dispersed in resin solutions have been developed.

Further, conductive films are manufactured by kneading various conductive materials into resin and using a calendering method, an extrusion method, or the like.

A nine-electroconductive film by casting has already been proposed by one of the present inventors (Japanese Patent Application No. 59-33).
No. 674).

The feature of the casting method is that it is easy to release the mold.
Unlike conventional methods, there is no unnecessary tension on the resulting film during manufacturing, and the film has a nearly uniform thickness.・、') Uniform dispersion and short time 0) There is no sedimentation during the period, and the conductive film is uniformly dispersed in the formed film, and it is free from variations in thickness a3 and non-uniform dispersion of the conductive material. The point is that there is no difference in conductivity at all in each part of the film formed.

Furthermore, as a human advantage, 7d, which cannot be manufactured using conventional methods,
: Thin film manufacturing is also possible.

However, when a whisker-shaped conductive material is used, if a large amount of conductive material is used, it becomes tangled in the liquid and becomes pill-like, which significantly deteriorates the surface condition of the cast film. In some cases.

<Means for solving the problem> In such cases, reducing the amount added reduces entanglement and improves the surface condition, but the desired conductivity may not be exhibited. In this case, use a method that reduces the amount of conductive material in the liquid without changing the ratio of conductive material and binder by using a binder resin with a polymerization degree of 1 to make it more diluted. It's okay.

When using 10 parts by weight or more of Neusker-like electrically conductive material per 100 weight parts of binder (1 resin), whiskers should be dispersed (or a strong shear should be added to the resin solution).
By partially destroying the whiskers on the same day as when the whiskers are disentangled and disentangled, a conductive film with a good surface condition can be obtained.

As a means for obtaining such a shear of 1 m force, a method generally used for pigment dispersion may be adopted.

This invention relates to a new conductive coating material in which newly developed conductive alkali metal titanate whiskers (manufactured by Daikyu Kagaku Co., Ltd., trade name Dentol) are dispersed in a resin liquid as a conductive material, and conductive coating materials using the same. casting film,
It is intended to provide electrically conductive materials such as electrically conductive composites.

<Function> The conductive alkali metal titanate whisker used in this invention has the following formula: (1) General formula M 20-a TL○su・bH20 (where M is an alkali metal such as Ljt- or K: O<a≦ 8
, ○≦b≦4.0<X<2; a, b and (■); or (2) = WU type M20 ・aTjoy ・bH20
(In the formula, M, aJ3 and b are the same as above: o<y≦2)
An alkali metal titanate whisker represented by is coated with one or more selected from η conductive metals and/or conductive metal oxides, metal halides, or other conductive metal compounds. (■) Two or (3) General formula M20-aTLOy-bH20 (in the formula M,
titanic acid represented by a, b and y)
When producing a group of alkali metal whiskers, one or more of the alkali metal titanate whiskers is mixed with one or more metal compounds such as conductive metal oxides, halides, carbonates, nitrates, or sulfur salts. In order to coexist with conductive metals and/or The alkali metal titanate whisker particles are coated with one or more selected from electrically conductive metal oxides, metal halides, or other conductive metal compounds, or at least the surface of the alkali metal titanate whisker particles is eutectic with them. A type of conductive alkali metal titanate whisker, such as those formed (■); Manoko is a mixture of two or more types.

The conductive alkali metal titanate whisker of the present invention is distinguished from the alkali metal titanate whisker (2) represented by the general formula: M2O-aTLO□.bH20 (a and b are as described above).

Regarding the electrically conductive alkali metal titanate whiskers in J3 of this invention, one of the inventors has already developed a method for producing electrically conductive alkali metal titanate whiskers (I) from alkali metal titanate whiskers (GV). Regarding the production method of conductive alkali metal titanate whisker (It) to conductive alkali metal titanate whisker fl) from LJ and conductive alkali metal titanate whisker (1), Although various inventions including manufacturing methods have been completed, the present inventors have
Roughly electrically insulating alkali metal titanate whisker σ
■As a method of imparting conductivity to the material, chemically coating the genuine material with a conductive metal and/or metal compound, or depositing or crystallizing the conductive metal and/or metal compound on its surface. The invention for obtaining η-electro-conductive alkali metal titanate whiskers has been completed. The present inventors have discovered that it is possible to economically impart conductivity by coating the surface of alkali metal titanate "Whisker GV" with a conductive material by chemical or physical treatment such as CVD or PVD. We have technically confirmed that it is possible.

In short, the conductive alkali metal titanate whiskers constituting the composition of the present invention are conductive materials with excellent reinforcing properties and deterioration resistance. As a starting material, it can be produced, for example, by various methods described below.

(i) Conductive alkali metal titanate whisker CI) Alkali metal titanate whisker N is prepared in a reducing atmosphere, for example, a reducing gas atmosphere such as hydrogen or in the presence of a reducing agent such as a carbon substance (.1). 300'C in an atmosphere of
A method of heat treatment above, preferably at 500'C or above;
Alternatively, when producing alkali metal titanate whiskers, the reaction is maintained in a reducing atmosphere or in a non-oxidizing atmosphere in the presence of a reducing agent.

In addition, in the alkali titanate represented by the general formula, M2O・aTLOx-bH20 (M, a, b, x are the same as above), M is potassium, that is, the general formula, K2O-aTjox・bH20 ( a, b, and x are the same as above), the color tone changes as X changes, and changes to white-purple, purple, black, black-purple, gold, silvery white, and The conductive alkali metal titanate whisker CI) according to the invention can be applied when X≦1.99, preferably x
<1.95, which exhibits a light purple to black color or more is preferable from the viewpoint of electrical conductivity.

(ii) η-electrolytic alkali metal titanate whiskers (I[
) This can be Ig'd by coating conductive alkali metal titanate whiskers (I) and/or hepta-alkali metal titanate whiskers (■) with an eta-conductive compound. Here, electroless plating, electroless plating,
Wet neutralization method, CVD, PVD4I: Any currently commonly used surface conductivity method can be applied, but the present inventors applied tin, indium, anti-septane, copper a3 to the surface of alkali metal titanate Riceker N. or a group of alkali metal titanate whiskers represented by the general formula K 20 ・aTLOy ・bH20 (a, b, and V are the same as above). , Nj, Cu, Pt, Ag
, Au, Cr, and Pd. In these cases, the general formula M20 ・ aTiOx @ bH20 (
The reduced titanate compound represented by M, a, b, and The coating means can be easily applied according to the law (-purpose,
L Useful and necessary. As a slightly different method, non>9 electrons P[
The surface of the alkali metal titanate whisker (IV) of
Conductive alkali metal titanate whiskers (Ill) with white collapsed conductivity can be obtained by coating with transparent electrocardial metal compounds such as tin oxide, antisulfur oxide, indium, or copper iodide. This is also useful in practice.

Qii) Conductive alkali metal titanate r Neusker fl
ll) These are the general formula, M2O・a Tj Oy
・When mounting nonorkali metal titanate whiskers of b 820 (M, a, b, and V are listed above), oxides, halides, carbonates, sulfates, and nitrates of tin, copper, silver, etc. etc., in the coexistence of titanium oxide as a titanium source or titanium hydroxide and an alkali metal as an alkali source or a halide at 500° to 1200°.
This can be achieved by heating with C or microwave. As a typical example, when titanium oxide is subjected to a melt reaction with potassium carbonate and tin chloride, white conductive potassium titanate metal whiskers with tin oxide precipitated on the surface of alkali metal titanate whiskers (whi 5kerS) are obtained. It will be done.

As above, typical conductive alkali metal titanate whiskers used in the present invention have been explained. )
or mixtures of two or more thereof, as well as reinforcing or non-reinforcing electrostatic ditanate alkali-devised whiskers. Usually fiber diameter 0.1-100μm, aspect]
A ratio of about 1 to 1000 is preferable from the viewpoint of imparting a reinforcing effect and surface smoothness. In particular, the raw materials for the conductive alkali metal titanate whiskers of this invention include fiber diameters of 0.2 to 0.5 μm and aspect ratios of 20 to 6.
Potassium titanate metal whiskers of about 0 are optimal. Potassium titanate metal whiskers endowed with electrical conductivity are the most suitable as the electrically conductive and alkali titanate whiskers of the present invention.

Generally, in the production of conductive coating agents, fine metal powder or GranoI 1-fine powder is added to a binder resin liquid and uniformly dispersed by stirring, but in the case of carbon black or metal oxide, , redispersion is performed depending on the purpose and use.

Conductive alkali metal titanate whisker (Ga 711) In order to improve the whisker-like structure, a binder (1) is added to the fat liquid and the whiskers get entangled with each other when only stirred, so when used as a coating agent, small pill-like particles are formed. There are many cases where small particles are seen on the surface of the coating, rubble, and the formed film, which is often unfavorable in terms of appearance.

However, it is also true that this whisker-like structure serves to further increase the conductivity. It is clear that a coating agent with less tangles must be obtained by using means to loosen the tangles or to lower the ratio to some extent.

Based on the above-1-, we will consider various dispersion methods (1)
In the end, this problem can almost be solved by adding conductive alkali metal titanate whiskers to the binder resin solution and using conventional pigment dispersion methods such as panes 1 to 1. became clear.

It is not clear how the conductive alkali metal titanate whiskers change during paint roll operation, but when the whiskers are untangled, the same
The same goes for destruction where the aspect ratio decreases to 1.1)
It is thought that it is in the middle of the day.

If necessary, binder resin liquid and solvent are added to the dispersion paste 1~ given in this way, and the conductivity (A to binder) or 29 conductivity (A to binder) with a constant ratio of 1 fat and a constant C degree]
-Adjust the ink agent.

There are no particular restrictions on the type of binder 1i (fat) used here, and it is necessary to select it depending on the L1 and usage.

When using a general spray paint, a vehicle for spray application may be used. In this case, it is preferable to increase the concentration of the paint and keep the viscosity high to prevent sedimentation of the material by diluting it during use.

When used as a conductive coating agent for Kires 1 to Sea 1, a coating agent that has an extremely high viscosity when used as a cast coating, usually 100 to 300 voids, and has conductive alkali metal titanate whiskers dispersed therein. shows titanium 1-robic properties, and almost no sedimentation is observed.

The conductive coating agent thus provided is applied to ingredients or processed into a film-like product, but its conductivity depends on the type d3 and the amount of σ of the conductive alkali metal titanate whiskers used, or is volume-specific. 100 in resistance
We accept a wide range of η electric 1] F from fat cm to insulator range.

Therefore, potential uses include electrostatic shielding, resistors, circuits, switch contacts, and electromagnetic shielding.Furthermore, because the conductive alkali metal titanate whiskers are chemically very stable, Baingu resin By selecting a suitable material, it can also be used as an electrode material for batteries.

As a specific application targeting electrostatic shielding, a coating agent using alkali metal titanate whiskers has been tested for floors and walls in clean rooms that require electrostatic shielding. , high rating 4
1 has been done.

<Example> This invention will be explained below with reference to Examples.

Note that all parts are parts by weight.

Example 1 100 parts of an acrylic surface treatment agent with a cL degree of 25% (manufactured by Seiko Kasei Co., Ltd., trade name Luxkin 594-2) and a conductive alkali metal titanate whisker (manufactured by Otsuka Kagakusha Co., Ltd., trade name Tentor WK-10) (1) After adding 50 parts and stirring uniformly, the mixture was passed through a paint roll 5 times while adding cyclohexanone as necessary.

As determined by a tube gauge, the particle size was 15 μm or less. The concentration of the paste produced was 45%.

Next, to 300 parts of a vinyl chloride-acrylic surface treatment agent (Seiko Kasei-Sou, trade name: Luxkin 101), 1 to 300 parts of the paste described above in (11) and 300 WIS of methyl ethyl ketone (MEK) were added, and the mixture was stirred uniformly to determine the concentration. O%'(-17Ct)S slightly gray 6-
A colored conductive coating was obtained.

This conductive coating agent was applied to a vinyl chloride sheet for wallpaper at a ratio of 309 if, and held at 180'C for 3 minutes.

The surface of the thus coated wallpaper was matte and slightly colored, giving it an excellent appearance for indoor use.

The surface resistance was 6 x 107 Ω74, and it was confirmed that the wallpaper had poor properties as an electrostatic shielding wallpaper.

Example 2 Polyurethane resin solution with a concentration of 25% and a viscosity of 600 poise (Seiko Kasei Seisou, trade name: Luxkin U-83-3)
> 200 parts of conductive alkali metal titanate whiskers (Daikyu Kagaku?t”A, trade name Tentol BK-20)
0) Add 100 parts of dimethylformamide (1
) M F ) was added and stirred uniformly, and then passed through a paint roll three times while adding DMF as necessary, to obtain 1 q of black-gray paste 1~ with a concentration of 42%.

56 parts of Sagi's polyurethane resin solution and 19 parts of DMF were added to 1 to 100 parts of this paste, stirred uniformly, and then filtered to defoam.

The conductive coating agent 1' and 1 had a viscosity of about 200 poise and a strong viscosity of 1 to 30%.

Using a doctor knife coater, apply this coating agent on the matte release pattern paper to a dry film thickness of 100 μm.
It was coated and dried at 80°C for 10 minutes and then at 120'C for 5 minutes. Thereafter, when the female pattern was peeled off, a black-blue conductive film with elasticity was obtained.

The electrocardiogram ↑1 of this membrane has the same volume resistance as 2.5X 10°QCm.

Example 3 According to Example 2, (j) Luxkin U-83- used in Example 2°C as a part of the conductive film with the release paper still attached.
A 20% solution of No. 3 was applied to give a dry film thickness of 100 μm, and dried at 80° C. for 6 minutes and then at 140° C. for 3 minutes. After that, the release paper was peeled off, and the conductive film with the two-layer structure was removed.
It's j7.

Unlike the conductive film obtained in Example 2, which was more susceptible to cracking, this conductive film did not tear easily due to the provision of the reinforcing layer.

The electrical resistance of the conductive layer was 2.8×10°Ωcm, and almost no decrease in conductivity was observed due to the provision of the reinforcing layer.

Example 4 Ten h-, IL/W k-100, 70 parts 83 J:
U I~, /L/ 65 parts of en Φ-combined vinyl chloride resin active water chemistry] - industry company! You, product name Smedica V)
The paste was added to 100 parts of a 35% solution of 100%, stirred uniformly, and then passed through a pane 1 to roll 3 times to form a 45% paste at a temperature of 1i7.

This paste J ~ and copolymerized vinyl chloride resin solution were mixed so that the ratio of conductive material to binder was as shown in Table 1 below, and after thorough stirring, d-seedling and 11-fold foaming were performed. Ta.

Next, each film was coated on matte release paper to a dry film thickness of 50 μm at 80°C (5 minutes, then dried at 120°C for 3 minutes, and after being left overnight, it peeled off from the release paper and became conductive. - Added 1 layer of h film.

When the conductivity of these conductive films was measured, the results shown in Table 1 were r<r, I.

Table 1 Example 5 Reinforce 1 q of the conductive coating agent obtained in Example 2 while drying. Dry at 120°C for 3 minutes and then at -120°C for 3 minutes.

The surface resistance was ε3×10 3 Ω/mouth.

Roughly coat this L with a drying Φ amount of 259 degrees, apply Unilac Ninin U-83-3, dry at 120 degrees Celsius for 333 minutes, and conductive. 1q of composite material.

Applicant's agent Patent attorney Kazu 1) Showa procedural amendment (voluntary) December 27, 1985 Patent Application No. 203002 of 1985 2 Title of invention Conductive coating agent and conductive material using the same 3
, Relationship to the case of the person making the amendment Patent applicant Address 1109 Ariku, Iyoya-cho, Nishi-ku, Kobe City Name Seiko Kasei Co., Ltd. (1 idiot) Specification 7
Contents of the amendment in the "Detailed Description of the Invention" column 1, page 4, line 14 of the specification letter, "such as conductive composite material" was corrected to "such as conductive composite material, conductive plastic molded product". .

2. On page 14, line 20, "electrostatic shield, resistor," is corrected to "electrostatic shield, electrostatic coating brimer for plastic molded products, resistor."

Claims (4)

[Claims] (1) A conductive coating agent comprising a binder resin, conductive alkali metal titanate whiskers, and a solvent. (2) A conductive material obtained by applying a conductive coating agent consisting of a binder resin, conductive alkali metal titanate whiskers, and a solvent onto a releasable base material and drying it. (3) Coating a conductive coating agent on the releasable base material,
3. The conductive material according to claim 2, wherein the conductive material obtained by drying is further coated with a conductive coating agent to form a multilayer structure. (4) A conductive material obtained by continuously coating a conductive coating agent consisting of a binder resin, conductive alkali metal titanate whiskers, and a solvent on a film-like substrate and drying it.